JPS61218605A - Process for manufacturing aqueous cut of ligand-free monomer/ meleic acid anhydride polymer, product thereby and coating composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides ligand-free monomers.
a process for solubilizing a maleic anhydride polymer and, more particularly, for making an aqueous cut of the polymer suitable for processing into a coating film with enhanced heat resistance and the process thus made. This is related to water-based cuts.

U.S. Pat. No. 4,358,573 discloses the use of an aqueous solution of ammonium hydroxide to solubilize terpolymers of maleic anhydride and mixtures of lower and higher alkenes. However, membranes made from such polymers lack enhanced heat resistance and may become viscous during storage and use.

In the past, zinc ammonium carbonate has been used as an additive to make cross-linked emulsion polymer compositions. As stated in US Pat. No. 4,339.370, zinc complexes were used for crosslinking, but not for dissolving and dispersing the polymer. U.S. Patent No. 3.320
, 196, zirconium complexes were used to disperse some alkali-soluble resins including rosin/maleic anhydride condensed with polyols.

The resulting polymers were used as removable coating compositions that exhibited enhanced water and detergent resistance while providing high gloss and hardness.

In U.S. Pat. No. 3,308,078.

Zinc ammonium acetate was used to aid in the dispersion of organic film formers in styrene-acrylate type multiligand emulsion polymers.

Heretofore, there has been a continuing need to provide resin coatings that impart superior heat resistance to the articles coated with them. Paper products such as paper plates and cups used for hot food products have required heat resistant coatings.

Additionally, marking materials containing resin binders such as inks and paints are required in the graphic arts field. Such marking materials may be applied to articles to provide information or decoration. however.

To date, marking materials have not had sufficient resistance to thermal loads during storage or use.

It is an object of the present invention to provide aqueous resin cuts of ligand-free monomer/maleic anhydride polymers suitable for formulating resin coatings with enhanced heat resistance.

The above objectives are achieved by a process for the production of water-based resin cuts that involves solubilization of a ligand-free monomer/maleic anhydride polymer in an aqueous medium with a metal fugitive ligand complex, where the metal is zinc or zirconium. .

Resin cuts made using the zinc or zirconium metal volatile ligand complexes of the present invention exhibited excellent heat resistance when formulated into coating films. Zinc or zirconium appears to act on cross-linking of the resin via the carboxyl group of hydrolyzed maleic anhydride.

The degree of heat resistance increase imparted to the coating ranges from 10°C (500F) to 38°C depending on the exact composition of the resin.
(100°F). The heat resistance imparted to coatings produced using the resin cuts of the present invention is particularly advantageous for graphic arts. Conventional graphic arts acrylic resins do not have special heat resistance and tend to stick or stick as temperatures increase.

In this process, the polymer to be solubilized is a copolymer, terpolymer or higher interpolymer.

Such polymers include maleic anhydride monomers as alternating units between units of other monomers.

As used herein, the term "maleic anhydride" refers to maleic anhydride monomer and methylmaleic anhydride, dimethylmaleic anhydride, fluoromaleic anhydride,
Other maleic anhydride derivatives such as methyl ethyl maleic anhydride or the hydrolyzed forms described above are included. The anhydride is preferably substantially free of acids and the like before the polymerization reaction. A preferred anhydride is maleic anhydride.

As used herein, the term "unliganded polymer" includes one or more comonomers that are polymerizable ethylenically unsaturated monomers. Representative such comonomers include alpha-olefins, aromatic Examples include group alkenyl monomers, acrylate monomers, and methacrylate monomers.

Representative aromatic alkenyl monomers include vinyltoluene, alpha-methylstyrene and styrene.

Representative acrylate and methacrylate monomers are listed in J.A., March 7, 1967.

R. No. 3,308,078, issued to J. R. Rogers et al. The disclosure of this patent, particularly columns 9 and 10 thereof, relates to ligand-free monomers and is specifically incorporated herein. As mentioned therein, the ligand-free monomers include alkyl acrylates and methacrylates.

Preferred comonomers polymerizable with maleic anhydride are:
These are known as 1-olefins, that is, α-olefins. Copolymers and terpolymers of maleic anhydride and 1-olefins are particularly suitable for forming the heat resistant coatings of the present invention. Maleic anhydride/α-olefin copolymers are described in U.S. Pat.
No. 553,177; No. 3.560,455; No. 3,5
No. 60,456; No. 3,560,457 and No. 3,4
No. 88,311, which is known in the art.

The most preferred ligand-free monomer(s)/maleic anhydride polymers solubilized by the process of the present invention are 7-maleic acid, C,-C,, lower 1-alkenes, and C1,-c,.

High a1-alkene terpolymers.

about 49 to 60 mole percent maleic anhydride, 1o
to 40 mole percent of lower 1-alkenes and higher 1-alkenes having 18 or more carbon atoms in their carbon chain4
It contains 0 to 10 mole percent. Such terpolymers are described in U.S. Pat.
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 3, No. 1, No. 1, No. 3, No. 1, No. 1, No. 1, No.

Preferred terpolymers generally have a number average molecular weight of about 3,000 to 5,000 and are described in U.S. Pat.
No. 553,177, Regrant No. 28.475, and No. 3,560,455.

Although the present resin cuts can be prepared at any concentration of resin present, in the aqueous cuts of the present invention, approximately 15 to 3
Preferably, 5% by weight resin is present. This resin cut can contain about 5 to 50% resin by weight.

Metal volatile ligand complexes are used to solubilize the polymers of the invention. The metal ion of this complex is zinc or zirconium ion. The volatile ligand is ammonia.

It easily converts to volatile gases. To make this complex, use formate, acetate, monobicarbonate.

Or preferably an anion such as carbonate is utilized.

This anion, such as carbonate or formate, is also volatile and easily converted to volatile gases such as hydrogen dioxide.

Suitable zinc and zirconium volatile ligand complexes include:
U.S. Patent Nos. 3,303,078 and 3,320,
No. 196. Preferred metal complexes are zirconium ammonium carbonate and zinc ammonium carbonate.

Generally, the metal volatile ligand complexes are prepared by addition of aqueous ammonia to an aqueous solution of zinc or zirconium salts.

If desired, zinc or zirconium oxides that are water insoluble can be dissolved in solutions such as ammonium carbonate, ammonium bicarbonate, ammonium formate, etc. in the presence of ammonia.

Generally, the concentration of metal volatile ligand complex in the aqueous cut is expressed as the ratio of moles of metal volatile ligand complex to equivalents of the carboxyl groups in the polymer of the invention to be dissolved. The metal ion to carboxyl group ratio is preferably about 0.075 to about 0.50.

Typically, the resin cuts are prepared by mixing one of the metal volatile ligand complexes of the present invention and the desired polymer in an aqueous solution at elevated temperatures until a dispersion is formed. If desired, the polymers of the present invention may be neutralized with a non-volatile alkaline substance such as sodium hydroxide, usually to up to about 40% of the carboxyl groups of the resin. It is preferred to include from about 3 to 20% by weight of the metal liquid complex, based on the weight of the final resin solution, although may also be used.

Most preferably, 10 to 17% by weight of the metal liquid complex is included.

Generally, when a coating composition is formulated from the resin cut, the coating composition will contain from about 0.30 to about 3.0% metal volatile ligand complex.

Generally, the metal volatile ligand complex lowers the pH of the solution to about 7.
It is added in an amount sufficient to make the number of The liquid medium is preferably water.

The following examples illustrate some preferred embodiments of the invention and are not intended to limit the scope of the invention.

Styrene of the present invention with a molar ratio of 0.610.4/1
A C,,α-olefin/maleic anhydride terpolymer was prepared and solubilized using zinc ammonium carbonate as described below.

Charge this α-olef interpolymer into a suitable container,
Subsequently, water and zinc ammonium carbonate solution were charged. Stir this mixture well and heat to 76℃~8℃.
The temperature was maintained at 2°C (1700F to 180°F) for 30 minutes or until all the resin went into solution. The solution was cooled to ambient temperature with stirring and then transferred to an isolated container for use. This resin cut had the following composition.

- 1 part 1 part - 1 plate Terpolymer - 20 Zinc ammonium carbonate solution (15%) 15 water
65 This resin cut was prepared as a coating as follows. This resin cut can be formulated into a coating by various methods. It can be used as is or can be combined with an acrylic emulsion at a level of O to 100% wet weight to enhance water resistance.

When this coating is compared to one using the same terpolymer but solubilized with ammonium hydroxide, the increase in heat resistance is 10°C to 38°C (50°C) when this composition is tested as described below. 'F to 100°F). Various coatings range from about 0.5 to about 2. OX 10″″Sm(0,2
The coating weight was tested by application onto a variety of paper stocks with dry film thicknesses ranging from 0.8 mils to 0.8 mils. The coating was allowed to dry for a minimum of 16 hours before testing. The heat resistance test was conducted using Sentinel Heat Sealer (S
Entinel Heat 5ealer)
Under a pressure of approximately 2.1 kg/am” (30 psi),
This was done with a residence time of 3 seconds. The samples were tested for coated surface versus coated surface and coated surface versus foil. The coating material is sticky (the adhesive may split or
The test was considered unsuccessful if the test resulted in adhesion (or adhesion such that the surface layer delamination occurred).

Cold Current 1-4 Resin cuts were prepared in the same manner as in Example 1 by solubilizing 25 parts of the terpolymer of Example 1, 10 parts of zinc ammonium carbonate solution, and 5 parts of ammonium hydroxide in 60 parts of water.

The resin cut thus produced had a pH of 7°9 and a pH of 4.
25cps Brookfield
d) It had viscosity. This resin cut was used directly as a coating and tested in the same manner as the coating of Example 1. The properties of this coating were as follows.

60 @ gloss meter reading = 47° ~ 49 @ maximum tack temperature - coated surface to coated surface: 232°C (450°
F) Maximum adhesion temperature - coated surface to foil = 288°C (550'
F) left m and a) 0, 5/0, 5/l, O and b) two types of styrene/c1° alpha olefin/maleic anhydride with a molar ratio of 0.410°6/1.0. Terpolymers were prepared and cut using the method of Example 1.

When these terpolymers were tested for heat resistance using the method of Example 1, they had the maximum adhesion temperatures shown below.

8232℃ (450'F) 288℃ (550'F
')b 219°C (425°F) 260
℃ (500'F) Procedural Amendment April 15, 1986 Michibe Uga, Commissioner of the Patent Office 1, Indication of the Case 1985 Patent Application No. 55174 2, Title of the Invention 3, Person Making Amendment Case Relationship with Patent Applicant Address Rice Consin, 53403, United States of America.

Racine, 15254 Hauer Street, Agent 5, Subject of amendment (1) "Detailed Description of the Invention" column of the specification (1) Delete "wetting" from page 14, line 15 of the specification.

Claims (1)

[Scope of Claims] 1. A process for producing an aqueous resin cut characterized by comprising solubilizing a ligand-free monomer/maleic anhydride polymer with a metal volatile ligand complex in an aqueous medium. 2. The process according to claim 1, wherein the metal volatile ligand complex is a metal ammonium complex selected from the group consisting of a zirconium ammonium complex and a zinc ammonium complex. 3. Process according to claim 2, characterized in that the complex is a metal ammonium carbonate selected from the group consisting of zirconium ammonium carbonate and zinc ammonium carbonate. 4. The process according to any one of claims 1 to 3, wherein the polymer is a terpolymer of a lower α-olefin, a higher α-olefin, and maleic anhydride. 5. The process according to any one of claims 1 to 3, wherein the polymer is a terpolymer of alpha olefin, styrene, and maleic anhydride. 6. A coating with improved heat resistance comprising a ligand-free monomer/maleic anhydride polymer, an effective amount of a metal volatile ligand complex and an aqueous medium, the composition having a pH of 7 to 9. Composition. 7. The composition of claim 6, wherein the polymer solution is present in an amount of about 80 to 97% by weight. 8. Claim 6 or 7, characterized in that the polymer is a terpolymer of a lower α-olefin, a higher α-olefin, and maleic anhydride.
The composition described in Section. 9. The composition according to claim 6 or 7, wherein the polymer is a terpolymer of α-olefin, styrene, and maleic anhydride. 10. The composition according to any one of claims 6 to 9, wherein the complex is a metal ammonium carbonate selected from the group consisting of zinc ammonium carbonate and zirconium ammonium carbonate.